Hydrogen peroxide formulations in barrier layer films with a metallized layer

ABSTRACT

The present disclosure concerns a cosmetic product for modifying the natural color of keratinous fibers, in particular human hair, comprising at least one packaging (VP) and a cosmetic composition (KM) contained in this packaging (VP). The packaging is made of a multi-layer film (F) comprising at least two polymer layers (P1) and (P2) and at least one barrier layer (BS). The cosmetic composition comprises at least one oxidizing agent and at least one thickening agent from the xanthane group. The use of the packaging (VP) in combination with the cosmetic composition (KM) does surprisingly not lead to an inflation of the packaging or an excessive water loss of the agent (KM) during storage.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a U.S. National-Stage entry under 35 U.S.C. §371 based on International Application No. PCT/EP2018/079795, filed Oct. 31, 2018, which was published under PCT Article 21(2) and which claims priority to German Application No. 10 2017 223 040.1, filed Dec. 18, 2017, which are all hereby incorporated in their entirety by reference.

TECHNICAL FIELD

The present disclosure is in the field of cosmetics and relates to a product for oxidative color change of keratinous fibers, in particular human hair, comprising an oxidant-containing composition packaged in a packaging. The oxidizing agent-containing composition comprises a thickening agent from the group of xanthanes. The packaging is manufactured from a special multi-layer film composite system, the wall of which comprises at least two polymeric layers and a barrier layer. The barrier layer has a permeation barrier effect for gases and water vapor. The barrier layer comprises a metal.

BACKGROUND

Changing the color of keratinous fibers, especially hair, is an important area of modern cosmetics. The appearance of the hair may be adapted to current fashion trends as well as to the individual wishes of each person. The expert knows various methods for changing the color of hair. The hair color may be changed temporarily by using direct dyes. In this process, already formed dyes diffuse from the dye into the hair fiber. Dyeing with direct dyes is associated with a low level of hair damage, but a disadvantage is the low durability and the fast washability of the colorations obtained with direct dyes.

If the consumer desires a long-lasting color result or a color shade that is lighter than the original hair color, oxidative color modifiers are usually used. For permanent, intensive colorations with corresponding fastness properties, so-called oxidative colorants are used. Such dyes usually contain oxidative colorant precursors, so-called developer components and coupler components, which form the actual dyes under the influence of oxidants—usually hydrogen peroxides. Oxidative colorants are exemplified by excellent, long-lasting dyeing results.

Oxidative color modifiers are usually marketed in the form of two-component agents, in which two different compositions are separately packaged in two separate packages and are not mixed together until shortly before use. The first composition is a formulation—usually acidic for stability reasons—which contains, for example, hydrogen peroxide in concentrations of from about 1.5 to about 12% by weight as an oxidizing agent. The oxidizing agent formulation is usually in the form of an emulsion or dispersion and is usually provided in a plastic bottle with a resealable outlet opening (developer bottle).

This oxidizing agent formulation is mixed with a second composition before use. This second composition is an alkaline formulation which is often in the form of a cream or a gel and which, if a color change is desired at the same time as the brightening, also contains at least one oxidative colorant precursor. This second composition may, for example, be provided in the form of a tube or in the form of a plastic or glass container.

In the usual application form described above, the second composition, which contains the alkalizing agent and/or the oxidative colorant precursors, is transferred from the tube or container into the developer bottle and then mixed by shaking with the hydrogen peroxide composition already in the developer bottle. In this way, the application mixture is prepared in the developer bottle. Application to the hair is then carried out via a small spout or outlet opening at the top of the developer bottle. The spout or outlet opening is opened after shaking and the application mixture may be removed by pressing the flexible developer bottle.

The use of the developer bottle requires a certain routine from the user, so that some users prefer to prepare the application mixture in a mixing bowl and apply it with a brush.

When preparing the application mixture in a bowl, both components—the first composition containing the oxidizing agent and the second composition containing an alkalizing agent and/or oxidative colorant precursors—are completely transferred into a bowl or similar vessel and stirred there, for example with the aid of a brush. The application mixture is then removed from the mixing bowl using the brush. With this form of application, the use of a voluminous and expensive developer bottle is not necessary, and the search continues for inexpensive and material-saving packaging forms for the oxidizing agent composition.

In this context, packages in pocket or bag form, which are usually made of plastic films or metal foils, are an inexpensive form of packaging with low material consumption.

Such packaging may be produced, for example, by gluing or hot pressing two plastic foils lying one on top of the other, with the gluing taking place on all edges of the foils. The interior of the packaging (i.e. the plastic bag) created by the bonding may then be filled with the desired cosmetic composition. The packaging may be opened by tearing or cutting open the plastic bag.

However, filling oxidizing agent compositions into such packaging is associated with problems caused by the reactivity of the oxidizing agent. Oxidizing agents are highly reactive substances which—depending on the storage conditions and the presence of decomposing impurities—decompose in small amounts and produce oxygen (i.e. gas).

The developer bottles known from the state of the art are usually only filled with the oxidizing agent composition to a maximum of half, usually only to a third of their internal volume. As a rule, developer bottles are made of polyethylene. Since polyethylene is permeable to both water vapor and other gases, there is no or only very slight excess pressure in the developer bottle. In addition, developer bottles are usually provided with strong, thick walls and a sturdy screw cap, so that the diffusion of water vapor or gases through the thickness of the walls is reduced and a slight increase in pressure within the bottle has no negative effects.

In contrast, bag-shaped packages are usually completely filled with the liquid composition, and there is practically no excess air space in the filled bag. In addition, such packages should be flexible, and when opened (e.g. torn open or cut open) there should be no uncontrolled escape of the composition. For this reason, when packaging liquid compositions, the creation of excess pressure in the package should be avoided if possible.

If an oxidizing agent composition is in such packaging, the gas (oxygen) produced during storage may cause the packaging to expand. Since the edges of the package are usually only glued together, in the worst case, strong inflation may lead to bursting of the packaging. For these reasons, when storing oxidizing agent-containing compositions, the choice of the film material of which the packaging is made is of great importance.

Packages made of pure plastic such as polyethylene or polypropylene are permeable to both water vapor and gases. When storing a composition containing oxidizing agents in a polyethylene or polypropylene package, the package does not expand. Due to the high permeability of the comparatively thin film of the packaging to water vapor, however, the water content of the composition is reduced. If the composition is stored in the packaging for several weeks or months, the water loss exceeds the maximum value permitted for adequate storage stability.

The production of suitable packaging for formulations containing hydrogen peroxide is a challenge. The above mentioned properties for the permeability of oxygen and water vapor have to be adjusted in such a way that a sufficient storage stability is given. The layer thickness of the film should be kept as low as possible for environmental reasons and to preserve resources. Furthermore, the layer thickness naturally also has an influence on the manufacturing costs. Against this background, thin layers are desired, but these do not always guarantee sufficient mechanical strength. If different materials are combined in a multi-layer film in order to satisfy a wide range of requirements, the manufactureability of the multi-layer film must also be guaranteed. Certain materials cannot be combined with each other because the cohesion between layers is not always sufficient or because their processing temperatures may be so different that joint processing is difficult.

Finally, the film materials are of great importance, especially when storing a multi-component system, as substances from the multi-component system can diffuse into the films and promote the detachment of layers forming the film. The choice of components of a hydrogen peroxide-containing formulation therefore also has an impact on the choice of packaging.

BRIEF SUMMARY

The instant disclosure provides a cosmetic product for modifying the natural color of keratinous fibers comprising

-   -   (i) at least one packaging comprising at least one multi-layer         film comprising at least one first polymer layer, at least one         second polymer layer and at least one barrier layer, and     -   (ii) at least one cosmetic composition packaged and included in         the packaging:         -   a) at least one oxidizing compound and         -   b) at least one thickening agent, selected from the group of             xanthanes,         -   wherein the first polymer layer is formed of polyethylene             terephthalate or polyethylene naphthalate; the second             polymer layer is formed of a polyolefin; and the barrier             layer is formed of metallized oriented polypropylene.

The objective of the present application was to package hydrogen peroxide-containing formulations in such a way that the mechanical strength of the packaging is sufficiently high to allow safe storage, but that easy access to the ingredients is guaranteed.

Surprisingly, it has now been found that oxidizing agent-containing compositions may be packaged where the water vapor permeability is low and inflation may be reduced by allowing the film to have a certain level of oxygen permeability. The films include a special film composite system and also have a barrier layer. By reducing the water vapor permeability, but adjusting the oxygen permeability to a sufficiently high level, the tendency to expand due to oxygen, which is formed from the hydrogen peroxide, is reduced and the mechanical strength is increased over time.

DETAILED DESCRIPTION

The following detailed description is merely exemplary in nature and is not intended to limit the disclosure or the application and uses of the subject matter as described herein. Furthermore, there is no intention to be bound by any theory presented in the preceding background or the following detailed description.

The subject-matter of the present disclosure is a cosmetic product for modifying the natural color of keratinous fibers, in particular human hair, comprising

-   -   (i) at least one packaging (VP) comprising at least one         multi-layer film (F) comprising at least one first polymer layer         (P1), at least one second polymer layer (P2) and at least one         barrier layer (BS), and     -   (ii) at least one cosmetic composition (KM) packaged and         contained in the packaging (VP):     -   a) at least one oxidizing compound and     -   b) at least one thickening agent selected from the group of         xanthanes,     -   wherein the first polymer layer (P1) is formed of polyethylene         terephthalate or polyethylene naphthalate, in particular         polyethylene terephthalate, the second polymer layer (P2) is         formed of a polyolefin, in particular polyethylene, and the         barrier layer (BS) is formed of metallized oriented         polypropylene.

Keratinous fibers, keratin-containing fibers or keratin fibers are furs, wool, feathers and in particular human hair. Although the products as contemplated herein are primarily suitable for lightening and dyeing keratinous fibers, there is nothing in principle to prevent their use in other areas.

The product as contemplated herein is a product for the oxidative color change of keratinous fibers, i.e. a product which is applied on the human head in order to achieve an oxidative coloring, a lightening, a bleaching or a color nuance of the hair. In this context, color nuance is understood to be a coloring in which the color result is lighter than the original hair color. That the product is to be used “to change the natural color” means that the product either comprises only an oxidizing agent for bleaching, or that the product comprises an oxidizing agent used with a coupler that is not part of the present disclosure to achieve a color change, or that the product is used with a dye that is not part of the present disclosure for further hair coloring.

Furthermore, the term “packaging” is understood to mean, as contemplated herein, a packaging which is preferably in the form of a sachet. A sachet is a small package in the form of a bag or pouch, which is often used in the packaging of cosmetics. The capacity of the packaging, in particular of the sachet, may, for example, be from about 5 to about 1000 ml, preferably from about 10 to about 200 ml and particularly preferably from about 20 to about

In addition, a multi-layer film (F) in the context of the present disclosure is understood to be a thin, flat and windable strip including the at least one polymer layer (P1) and the at least one polymer layer (P2). This multi-layer film (F) forms the wall of the packaging (VP). The packaging also comprises a barrier layer (BS), which selectively permits or reduces the passage of water vapor and other gases such as oxygen.

Furthermore, in the context of the present disclosure, the term “thickening agent” is to be understood as meaning compounds which can bind liquids, in particular water, and increase the viscosity of these liquids. In the context of the present disclosure, this also includes gelling agents which are capable of thickening liquids into compositions with a gel-like consistency or into gels. As contemplated herein, gel-like cosmetic products or gels are dimensionally stable, easily deformable disperse systems including at least two components, the gelling agent (usually a solid, colloidal substance with long or strongly branched compounds) and a liquid (usually water) as dispersant. The gelling agent forms a spatial network in the liquid, whereby the individual gel-forming compounds adhere to one another at different spatial points by major and/or minor valences.

As contemplated herein, the permeability values of the film (F) are advantageously adjusted. The film (F) thus imparts advantageous barrier properties to the packaging, especially with respect to the permeability for water vapor: Water Vapor Transmission Rate (WVTR) measured in the unit g/(m² d) or g/(m²24 h) measured according to the ASTM F 1249 method at about 38° C. ambient temperature and about 100% relative humidity, and for oxygen Oxygen Transmission Rate (OTR), measured in cm³/(m² d bar) or cm³/(m²24 h), where cm³ is equal to cc, at an atmospheric pressure of 1 bar measured according to ASTM D 3985 at about 23° C. ambient temperature and about 50% relative humidity.

The term “xanthanes” refers to polysaccharides which, as contemplated herein, occur naturally and may be obtained from sugar-containing substrates with the aid of bacteria of the genus Xanthomonas. Preferably, xanthane used as contemplated herein contains d-glucose, d-mannose, d-glucuronic acid, acetate and pyruvate in a molar ratio of about 28:30:20:17:5.1-6.3, the main chain including β-1,4-bonded glucose units (also called cellulose chain). The xanthanes which are particularly preferred in the context of the present disclosure have the CAS No. 11138-66-2 and the following structural formula:

The cosmetic product as contemplated herein comprises as first component a packaging (VP) comprising at least one multi-layer film (F). This film comprises at least one first polymer layer (P1), at least one second polymer layer (P2) and at least one barrier layer (BS). This multi-layer film forms the wall or outer shell of the packaging. As described above, such packaging is usually made by gluing, pressing or welding two pieces of film on top of each other (the packaging (VP) is filled with the cosmetic composition (KM) at the same time). i.e. such packaging is closed at all edges. This packaging may be opened, for example, by tearing or cutting it open.

The thickness of the multi-layer film (F) determines the mechanical properties and the strength of the films. It should be designed in such a way that there is sufficient mechanical stability, but at the same time the film (F)—and thus the packaging (VP) produced from the film—should be flexible enough to allow complete removal of the cosmetic composition (KM) from the opened packaging (VP) by pressing or squeezing. A film meets these requirements if the film (F) has a certain total thickness. Preferred embodiments of the present disclosure include at least one multi-layer film having a total thickness of from about 28 μm to about 220 μm, preferably of from about 52 μm to about 180 μm, more preferably of from about 80 μm to about 140 μm. For the purposes of the present disclosure, the total thickness of the film (F) is understood to be the sum of the thicknesses of all individual layers that the film (F) includes.

The configuration of layers (P1), (P2) and (BS) within the multi-layer film (F) may be different. Furthermore, it is also possible that the film (F) includes further layers in addition to the layers mentioned above. In addition, as contemplated herein, it is advantageous if all the previously mentioned layers are oriented parallel to the surfaces of the film (F), i.e. all layers have the same orientation. If the multi-layer film (F) contains the three layers (P1), (P2) and (BS) described above, the following layouts of the layers would be possible (viewed from the interior (in contact with the cosmetic composition (KM)) to the exterior):

-   -   a) *Interior*-Layer (P1)-Layer (P2)-Barrier layer         (BS)-*Exterior*,     -   b) *Interior*-Layer (P1)-Barrier layer (BS)-Layer         (P2)-*Exterior*,     -   c) *Interior*-Layer (P2)-Layer (P1)-Barrier layer         (BS)-*Exterior*,     -   d) *Interior*-Layer (P2)-Barrier layer (BS)-Layer         (P1)-*Exterior*,     -   e) *Interior*-Barrier layer (BS)-Layer (P1)-Layer         (P2)-*Exterior*,     -   f) *Interior*-Barrier layer (BS)-Layer (P2)-Layer         (P1)-*Exterior*.

However, as contemplated herein, it is preferred when the barrier layer (BS) is located between the first polymer layer (P1) and the second polymer layer (P2), the second polymer layer (P2) being located on the exterior of the package. In this case, the multi-layer film (F) is composed of three layers, layer (P1) being at the innermost and in contact with the cosmetic composition (KM). Layer (P1) is in contact with the barrier layer (BS), and the barrier layer (BS) is in contact with layer (P2). In this layer, the layers (P1) and (P2) are not adjacent to each other but are separated by the barrier layer (BS). The particular advantage of this configuration is that the—often very thin—barrier layer (BS) is not located on either the inner or outer surface of the multi-layer film (F), but is protected by the polymeric layer (P1) towards the inside and by the polymeric layer (P2) towards the outside. In this way, mechanical abrasion or destruction of the barrier layer (BS) may be avoided as far as possible. It is therefore advantageous in the context of the present disclosure if the at least one multi-layer film (F) contains the at least one barrier layer (BS) between the at least one first polymer layer (P1) and the at least one second polymer layer (P2). The use of such packaging has been shown to be particularly advantageous in terms of increased storage stability, as this layout avoids mechanical abrasion or destruction of the barrier layer (BS) as much as possible. In a further preferred embodiment, the barrier layer (BS) is also located between the two polymer layers P1 and P2, but the first polymer layer (P1) is located on the exterior of the package.

As contemplated herein, the exterior of the packaging (VP) is understood to be that side of the packaging which does not come into contact with the cosmetic composition (KM) but with the environment. The use of such packaging has proven to be particularly advantageous in terms of increased storage stability, as this layout shows neither swelling nor delamination during prolonged contact with an oxidizing agent-containing composition.

The first polymeric material of the first layer (P1) is, as contemplated herein, a polyester. This material may be a layer of one polymer type or a layer of a polymer blend. According to the present disclosure, the at least one first polymer layer (P1) is formed from polyethylene terephthalate or polyethylene naphthalate, in particular from polyethylene terephthalate. As contemplated herein, the term “formed” is understood to mean that the polymer layer contains at least about 70% by weight, preferably at least about 80% by weight, more preferably at least about 90% by weight, most preferably at least about 99% by weight, in each case based on the total weight of the polymer layer (P1), of the above-mentioned compounds.

Polyethylene terephthalate (PET) is a polymer from the polyester group. Polyethylene terephthalate may be produced, for example, by transesterification of dimethyl terephthalate with ethylene glycol at higher temperatures. In this transesterification reaction, methanol is split off, which is removed by distillation. The resulting bis(2-hydroxyethyl)-terephthalate is converted to PET by polycondensation, again producing ethylene glycol. Another method of producing polyethylene terephthalate is the direct polycondensation of ethylene glycol and terephthalic acid at high temperatures with distillation of the resulting water. Polyethylene terephthalate is exemplified by a particularly high mechanical strength. If the PET layer forms the outer layer, this also offers the advantage that the layers underneath may be printed without the print being rubbed off. The PET layer is transparent and provides a mechanical protective layer for the printed layer.

According to a preferred embodiment of the present disclosure, the layer thickness of the first polymer layer (P1) is from about 4 μm to about 50 μm, preferably from about 5 μm to about 35 μm, more preferably from about 6 μm to about 20 μm. The layer thickness of the PET layer used according to the preferred embodiment of the present disclosure is associated with special advantages, which are related to general properties of PET. PET is exemplified by high dimensional stability/stiffness. If PET with these layer thicknesses is chosen as the first polymer layer (P1), this offers an advantageous mechanical dimensional stability for the film. At the same time, the overall thickness of the film may be kept low, so that a material and resource-saving film may be provided.

Furthermore, the multi-layer film (F) from which the package is made comprises a second polymer layer (P2) of a second polymeric material. The second polymeric material may be a layer of one type of polymer or a layer of a polymer mixture. It is provided in the context of the present disclosure that the at least one second polymer layer (P2) is formed of a polyolefin, in particular of polyethylene. As contemplated herein, the term “formed” is understood to mean that the polymer layer comprises at least about 70% by weight, preferably at least about 80% by weight, more preferably at least about 90% by weight, in particular at least about 99% by weight, each relative to the total weight of the polymer layer (P2) of the aforementioned compounds.

The second polymeric material of the second layer (P2) of the multi-layer film (F) is a polyolefin, in particular polyethylene. Polyolefins are polymers which are produced from alkenes such as ethylene, propylene, 1-butene or isobutene by chain polymerization. Polyolefins are saturated hydrocarbons. They are semi-crystalline thermoplastics which are easy to process. They are exemplified by good chemical resistance. Polyethylene and polypropylene are widely used in film applications. As contemplated herein, polypropylene is therefore used for the second layer (P2), but polyethylene is preferred. Polyethylene is produced by polymerization of ethylene using various catalysts. For example, polyethylene may be produced by polymerizing ethylene in the gas phase or in suspension. The average relative molar mass may be controlled, for example, by adjusting a certain hydrogen partial pressure during the polymerization of ethylene. Polyethylene may be processed by extrusion and stretch blow molding, or by pressing, calendering, thermoforming and cold forming.

The second polymer layer (P2) serves as a supporting layer. Although polyethylene has the disadvantage of being permeable to oxygen and water vapor, it has the advantage of being inexpensive and, due to its low melting point—lower than that of polypropylene—it is easy and energy-saving to process.

According to a preferred embodiment of the present disclosure, the second polymer layer (P2) has a certain layer thickness. According to the preferred embodiment of the present disclosure, the second polymer layer (P2) has a layer thickness of from about 20 μm to about 150 μm, preferably of from about 30 μm to about 110 μm, more preferably of from about 40 μm to about 90 μm. In particular, the second polymer layer (P2) has a higher layer thickness than the first polymer layer (P1).

The polymer layers (P1) and (P2) of the multi-layer film (F) comprise organic polymeric materials, which generally have only an insufficient barrier effect against gases and water vapor. If the oxidizing agent-containing composition (KM) is packaged in a packaging (VP) made of a multi-layer film (F), which only comprises the two organic polymer layers (P1) and (P2), water vapor may escape unhindered, so that the water content in the composition (KM) changes in an unacceptable way during longer storage. To minimize the uncontrolled escape of water vapor from the packaging (VP), the organic polymer layers (P1) and (P2) are therefore used in combination with a barrier layer (BS).

The barrier layer (BS) has a passage barrier effect for gases and water vapor. As contemplated herein, this means that the barrier layer (BS) reduces and controls the permeation rate of water vapor and gases through the film. A film (F) as contemplated herein, which has a barrier layer (BS) in addition to the layers (P1) and (P2), thus has a reduced water vapor permeability and a reduced gas permeability compared to a comparable film (with the same overall thickness), which only has the two layers (P1) and (P2) but no barrier layer (BS).

For example, the barrier layer (BS) is a thin layer comprising an inorganic material, which may be applied to organic polymer layers using vapor deposition techniques (e.g. PVD “physical vapor deposition” or CVD “chemical vapor deposition”).

If the barrier layer (BS) is a layer comprising at least one inorganic material, then the films may be made of metals, semi-metals or metal or semi-metal oxides, for example aluminum, aluminum oxides, magnesium, magnesium oxides, silicon, silicon oxides, titanium, titanium oxides, tin, tin oxides, zirconium, zirconium oxide and/or carbon.

As contemplated herein, the barrier layer (BS) is made of metallized, oriented polypropylene. Polypropylene is alternatively also known as poly(l-methylethylene), and is a thermoplastic polymer belonging to the group of polyolefins. Polypropylene is produced by polymerization of propylene (propene) using various catalysts. For example, polypropylene can be produced by stereospecific polymerization of propylene in the gas phase or in suspension according to Giulio Natta. Polypropylene as contemplated herein may be isotactic and thus highly crystalline, but also syndiotactic or amporphous. The average relative molar mass may be controlled, for example, by adjusting a certain hydrogen partial pressure during the polymerization of the propene. For example, polypropylene may have average relative molar masses of approx. 150,000 to about 1,500,000 g/mol. Polypropylene may be processed by extrusion and stretch blow molding, or by pressing, calendering, thermoforming and cold forming.

An oriented polypropylene is defined by the expert as a polypropylene film which is stretched during production after an extrusion or calendering step, namely stretched in the direction of extrusion and/or stretched at about 90° to the direction of extrusion. The film is preferably stretched in both directions, i.e. films in which the barrier layer—or the entire film—is biaxially stretched, particularly preferably simultaneously biaxially. During the stretching step the polymeric material is oriented. This is of great importance for the properties of the film layer, especially in the case of polypropylenes, since the orientation step determines the shape of the crystalline domains of the polymeric material and thus the physical properties of the film.

The polypropylene film is metallized. Possible metals are the above mentioned metals aluminum, magnesium, silicon, titanium, tin, and zirconium, especially aluminum. The metals are evaporated onto the carrier film. According to a preferred embodiment of the present disclosure, the ratio of the layer thickness of metal to oriented polypropylene is from about 1:1000 to about 1:10, preferably from about 1:500 to about 1:50, more preferably from about 1:200 to about 1:100.

The production of films with barrier layers comprising inorganic material is known. Also the multi-layer film (F) used in accordance with the present disclosure may be manufactured by a process which is used for the manufacture of known films with barrier layers in the state of the art, as described for example in the documents EP 1036813 A1, EP 2371539 A1 and EP 1541340 A1.

The barrier layer (BS) may additionally include a thin layer of inorganic-organic hybrid polymers. These polymers are known in the literature under the technical term ORMOCER polymers. A typical ORMOCER polymer may be produced, for example, by hydrolytic polycondensation of an organo-functional silane with an aluminum compound and possibly with an inorganic oxide component. Corresponding syntheses are disclosed in EP 0792846 B 1, which is referred to in full here. Inorganic-organic hybrid polymers (ORMOCER polymers) have both inorganic and organic network structures. The inorganic silicate network structure may be formed in the sol-gel process by controlled hydrolysis and condensation of alkoxysilanes. The silicate network may be specifically modified by including metal alkoxides in the sol-gel process. By polymerization of organo-functional groups, which are introduced into the material by the organoalkoxylanes, an additional organic network is built up. The ORMOCER polymers produced in this way may be applied to layers (P1) and/or (P2) using conventional application techniques (spraying, brushing, etc.).

The thicker the barrier layer (BS), the greater or stronger the barrier effect against the passage of gases and water vapor. The thickness of the barrier layer (BS) may therefore be selected depending on the desired barrier effect. According to a preferred embodiment of the present disclosure, the at least one barrier layer (BS) has a layer thickness of from about 4 μm to about 25 μm, preferably of from about 5 μm to about 20 μm, more preferably of from about 6 μm to about 18 μm.

The material, structure and layer thicknesses determine the permeability values of the film. The multi-layer film (F) of the packaging of the cosmetic product as contemplated herein is exemplified by advantageous properties with regard to oxygen permeability and water vapor permeability. The multi-layer film exhibits an oxygen transmission rate (OTR) at about 23° C. and about 50% relative humidity of from about 0.1 to about 5 cc/m²/d/bar, preferably from about 0.2 to about 3.5 cc/m²/d/bar, more preferably from about 0.5 to about 2.5 cc/m²/d/bar, and a water vapor transmission rate at about 38° C. and about 100% relative humidity of from about 0.1 to about 5 g/m² d, preferably from about 0.2 to about 3.5 g/m² d, more preferably from about 0.5 to about 2.5 g/m² d.

As contemplated herein, the permeability values of the film (F) are advantageously adjusted. The film (F) thus imparts advantageous barrier properties to the package, especially with regard to the permeability for water vapor: Water Vapor Transmission Rate (WVTR) measured in the unit g/(m² d) or g/(m²24 h) measured according to the ASTM F 1249 method at about 38° C. ambient temperature and about 100% relative humidity, and for oxygen: Oxygen Transmission Rate (OTR) measured in cm³/(m² d bar) or cm³/(m²24 h), where cm³ is equal to cc, at an atmospheric pressure of about 1 bar measured according to ASTM D 3985 at about 23° C. ambient temperature and about 50% relative humidity.

In addition to the layers (P1), (P2) and (BS) described so far, the multi-layer film (F) may additionally comprise one or more further layers. These additional layers may, for example, be intermediate layers and/or adhesive layers. It is therefore preferred as contemplated herein if the at least one multi-layer film (F) additionally contains at least one further layer selected from the group of intermediate layers (SZ), adhesive layers (SK) and mixtures thereof.

For example, the films (F) may have further intermediate layers (SZ) to increase the mechanical stability. Intermediate layers may also prevent or minimize the permeation of polymers or remaining monomers from a polymer layer into the cosmetic composition (KM).

To increase bond strength, the films may also comprise one or more adhesive layers (SK) to reduce or prevent delamination (i.e. peeling or formation of an air space) between two layers.

A particularly preferred product as contemplated herein is the multi-layer film (F) comprises, in addition to the first polymer layer (P1), the second polymer layer (P2) and the barrier layer (BS), one or more further layers selected from intermediate layers (SZ) and/or adhesive layers (SK).

If the multi-layer film (F) contains other layers in addition to the layers (P1), (P2) and (BS), the following layouts of the layers are possible (from interior (in contact with the cosmetic composition (KM)) to exterior):

-   -   a) *Interior*-Layer (P1)-First adhesive layer (SK1)-Layer         (P2)-Second adhesive layer (SK2)-Barrier layer (BS)-*Exterior*,     -   b) *Interior*-Layer (P1)-Adhesive layer (SK1)-Layer (P2)-Barrier         layer (BS)-*Exterior*,     -   c) *Interior*-Layer (P1)-Layer (P2)-Second adhesive layer         (SK2)-Barrier layer (BS)-*Exterior*,     -   d) *Interior*-Barrier layer (BS)-First adhesive layer         (SK1)-Layer (P1)-Second adhesive layer (SK2)-Layer         (P2)-*Exterior*,     -   e) *Interior*-Barrier layer (BS)-Adhesive layer (SK)-Layer         (P1)-Layer (P2)-*Exterior*,     -   f) *Interior*-Barrier layer (BS)-Layer (S1)-Adhesive layer         (SK)-Layer (P2)-*Exterior*,     -   g) *Interior*-Layer (P1)-First adhesive layer (SK1)-Barrier         layer (BS)-Second adhesive layer (SK2)-Layer (P2)-*Exterior*,     -   h) *Interior*-Layer (P1)-Adhesive layer (SK)-Barrier layer         (BS)-Layer (P2)-*Exterior*,     -   i) *Interior*-Layer (P1)-Barriere Layer (BS)-Adhesive layer         (SK)-Layer (P2)-*Exterior*

In any case, the film should be designed so that there is sufficient adhesion between the films. According to a preferred embodiment of the present disclosure, the bond strength of the film is from about 0.1 to about 10 N/15mm, preferably from about 1 to about 8 N/15mm, more preferably from about 1.5 to about 5 N/15mm This is measured by the ASTM F-904 method. The bond strength is a physical measure of the adhesive force between the layers. It is related to the two layers of a film with the lowest bond strength between two layers of the same film. The adhesive strengths set as contemplated herein result in a favorable mechanical stability over the storage time of the packaged cosmetic product.

Also, the strength between two bonded (sealed or sealed-off) films should be sufficient. According to a preferred embodiment of the present disclosure, the seal strength of the packaging (VP) is from about 10 to about 40 N/15mm, preferably from about 15 to about 35 N/15mm, more preferably from about 20 to about 30 N/15mm, under the conditions of about 150° C., about 2.54 cm (1″) and about 4 kg/cm2. The seal strength is measured according to ASTM F-88 under the above conditions. The challenge with packaging is always to ensure the mechanical durability of the packaging while at the same time making the contents easily accessible to the user. Adjusting the seal strength to these values enables both of these objectives to be achieved.

The term sealed seam refers to a seam by which the package is closed. Usually, two films are placed on top of each other for closing the package and are pressed together by a force perpendicular to the film surface. By heating the films in the area that is being compressed, parts of the compressed areas may fuse together, so that the films are welded together. There may also be an adhesive between the compressed films that strengthens the seam.

The product as contemplated herein comprises as a second component a cosmetic composition (KM) which is packaged in the packaging (VP) and contains at least one oxidizing agent and a thickening agent from the group of xanthanes.

The intended use of the product as contemplated herein is oxidative color change. For this purpose—as already described above—a cosmetic composition (KM) containing an oxidizing agent is usually mixed with a second composition (B) which is prepared separately from (KM). In this way, the ready-to-use oxidative color changing agent is produced. Depending on whether the oxidative color change is intended to achieve a bleaching, brightening or coloring effect, the composition (B) may contain different ingredients. If pure lightening or bleaching is to be achieved, composition (B) contains at least one alkalizing agent. If oxidative coloration is desired, the composition (B) often contains the oxidative colorant precursors in addition to the alkalizing agent. In order to ensure that the compositions (KM) and (B) may be mixed sufficiently quickly, both the composition (KM) and the composition (B) are usually free-flowing, aqueous or water-containing compositions.

As contemplated herein, the composition (KM) is an aqueous composition. The water content of the composition (KM) may, for example, be from about 60 to about 97% by weight, preferably from about 75 to about 93% by weight, more preferably from about 78 to about 91% by weight, in particular from about 80 to about 88.0% by weight, based on the total weight of the composition (KM). All weight data in % by weight refer to the total weight of water contained in the composition (KM), which is set in relation to the total weight of the composition (KM).

The cosmetic composition (KM) contains as first essential ingredient a) at least one oxidizing agent. Preference is given to certain oxidizing agents. It is therefore advantageous in the context of the present disclosure if the cosmetic composition (KM) contains at least one oxidizing compound selected from the group of persulfates, chlorites, hydrogen peroxides and attachment products of hydrogen peroxides to urea, melamine and sodium borate, in particular hydrogen peroxides. As contemplated herein, the use of hydrogen peroxide has proven to be particularly advantageous.

The concentration of the oxidizing agent in the composition (KM) is determined on the one hand by the legal requirements and on the other hand by the desired effect; preferably from about 0.5 to about 20.0% by weight solutions in water are used. Therefore, it is found to be preferred if the cosmetic composition (KM) contains at least one oxidizing compound, in particular hydrogen peroxide, in a total amount of from about 0.1 to about 10% by weight, preferably from about 0.2 to about 8.0% by weight, preferably from 0.2 to 7.0% by weight, in particular from about 0.2 to about 6.0% by weight, based on the total weight of the cosmetic composition (KM). The higher the content of oxidizing agent, in particular hydrogen peroxide, in the composition (KM), the greater is the amount of gas produced in the case of a proportional decomposition of the oxidizing agent. Compositions containing a higher concentration of oxidizing agent are therefore much more difficult to package in packaging (VP) than compositions containing a lower concentration of oxidizing agent. The amount of hydrogen peroxide refers to about 100% hydrogen peroxide.

In the course of the work leading to this present disclosure, it was found that the product as contemplated herein is particularly suitable for the packaging and stable storage of higher concentrated hydrogen peroxide compositions (KM). Thus, packaging (VP) as contemplated herein, which contained compositions (KM) with from about 9 to about 12% by weight of hydrogen peroxide, showed no changes in volume (i.e. no swelling) and no unplanned openings (i.e. the packages did not burst open) even after storage at elevated temperature for several weeks.

The cosmetic composition (KM) contains as the second essential ingredient b) at least one thickening agent from the group of xanthanes. The use of xanthanes has proved to be particularly advantageous since they ensure sufficient thickening over a long period of time even under highly acidic conditions and in the presence of an oxidizing agent. The thickening ensures a good handling of the cosmetic composition (KM). In order to ensure sufficient thickening, at least one thickening agent is preferably used in certain quantity ranges. It is therefore advantageous in the context of the present disclosure if the cosmetic composition (KM) contains the at least one thickening agent selected from the group of xanthanes in a total amount of from about 0.1 to about 10% by weight, preferably of from about 0.2 to about 8.0% by weight, more preferably of from about 0.2 to about 7.0% by weight, in particular of from about 0.2 to about 6.0% by weight, based on the total weight of the cosmetic composition (KM). In the context of the present disclosure, the use of xanthanes, which have an average particle diameter D50 of from about 140 to about 200 μm and a viscosity (about 0.3% by weight solution in about 0.3% KCl) of from about 250 to about 800 mPa·s (measured with Brookfield viscometer at about 3 rpm), has proved useful. Such xanthanes are commercially available under the trade name Keltrol CG-SFT from CP Kelco, for example.

In the course of the work leading to this present disclosure, it has been found that by using the aforementioned special thickening agent, the cosmetic composition (KM), which contains at least one oxidizing agent, may be packaged and stored in the special packaging (VP) without this packaging—which has a barrier layer with a passage barrier effect for gases and water vapour—expanding or bursting.

In this context, a very specific combination of oxidizing agent and thickening agent has proven to be advantageous. The product as contemplated herein is therefore exemplifiedin a preferred embodiment in that the cosmetic composition (KM) contains hydrogen peroxide as well as xanthane.

For further optimization of the storage stability, the above mentioned compounds are preferably used in certain quantity ranges in the composition (KM). Particularly preferred embodiments are exemplified in that the cosmetic composition (KM) comprises

-   -   a) from about 1.5 to about 15% by weight of hydrogen peroxide         and     -   b) from about 0.2 to about 6.0% by weight of xanthane, each         based on the total weight of the cosmetic product (KM).

The cosmetic composition (KM) preferably has an acidic pH value in order to avoid or reduce decomposition of the oxidizing agent used, in particular the hydrogen peroxide. It is therefore preferred in the context of the present disclosure that the cosmetic composition (KM) has a pH value (measured at about 20° C.) of from about pH 1.5 to about pH 5.0, preferably of from about pH 2.0 to about pH 4.7, more preferably of from about pH 2.3 to about pH 4.4, in particular of from about pH 2.5 to about pH 4.

The composition (KM) contained in the packaging (VP) contains the essential ingredients in an aqueous or aqueous-alcoholic carrier, which may be a cream, an emulsion, a gel or a surfactant-containing foaming solution. In order to achieve the desired properties of these dosage forms, the composition (KM) may also contain additional active ingredients, auxiliary substances and additives.

The composition (KM) may also contain one or more acids to stabilize the oxidizing agent used, especially the hydrogen peroxide. It is therefore preferred in the context of the present disclosure if the cosmetic composition (KM) additionally contains at least one acid selected from the group of dipicolin acid, lemon acid, vinegar acid, apple acid, milk acid, wine acid, salt acid, phosphorus acid, pyrophosphor acid and their salts, benzoe acid and salts thereof, 1-hydroxyethane-1,1-diphosphonic acid, ethylenediaminetetraacetic acid and salts thereof, sulfuric acid and mixtures, in particular a mixture of dipicolin acid, disodium pyrophosphate, ethylenediaminetetraacetic acid and salts thereof and 1-hydroxyethane-1,1-diphosphonic acid.

A particularly high stabilization of the oxidizing agent, in particular of the hydrogen peroxide, is achieved if the above-mentioned acids are used in specific amounts. It is therefore advantageous in this context if the at least one acid, in particular the mixture of dipicolin acid, disodium pyrophosphate, ethylenediaminetetraacetic acid and its salts and 1-hydroxyethane-1,1-diphosphonic acid, is contained in a total amount of from about 0.1 to about 3.0% by weight, preferably of from about 0.5 to about 2.5% by weight, more preferably of from about 0.8 to about 2.0% by weight, in particular of from about 0.9 to about 1.5% by weight, based on the total weight of the cosmetic composition (KM)

The following tables show particularly preferred forms AF 1 to AF 16 of the cosmetic composition (KM) contained in the packaging (VP) (all figures in % by weight, unless otherwise indicated).

AF 1 AF 2 AF 3 AF 4 Oxidizing agent 0.5-20 1.0-18  1.2-16  1.5-15  Xanthane 0.1-10 0.2-8.0 0.2-7.0 0.2-6.0 Cosmetic carrier ¹⁾ ad 100 ad 100 ad 100 ad 100

AF 5 AF 6 AF 7 AF 8 Oxidizing agent ²⁾ 0.5-20 1.0-18  1.2-16  1.5-15  Xanthane 0.1-10 0.2-8.0 0.2-7.0 0.2-6.0 Cosmetic carrier ¹⁾ ad 100 ad 100 ad 100 ad 100

AF 9 AF 10 AF 11 AF 12 Oxidizing agent ²⁾ 0.5-20 1.0-18 1.2-16  1.5-15  Xanthane 0.1-10  0.2-8.0 0.2-7.0 0.2-6.0 Acid  0.1-3.0 0.50-2.5  0.8-2.0 0.9-1.5 Cosmetic carrier ¹⁾ ad 100 ad 100 ad 100 ad 100

AF 13 AF 14 AF 15 AF 16 Oxidizing agent ²⁾ 0.5-20 1.0-18 1.2-16  1.5-15  Xanthane 0.1-10  0.2-8.0 0.2-7.0 0.2-6.0 Acid ³⁾  0.1-3.0 0.50-2.5  0.8-2.0 0.9-1.5 Cosmetic carrier ¹⁾ ad 100 ad 100 ad 100 ad 100

-   -   ¹⁾ Aqueous or aqueous-alcoholic carrier     -   ²⁾ Hydrogen peroxide, amount calculated on about 100% hydrogen         peroxide,     -   ³⁾ Selected from a mixture of dipicolin acid, disodium         pyrophosphate and 1-hydroxyethane-1,1-diphosphonic acid.

The previously described embodiments AF 1 to 16 are each packaged in packaging (VP) with the following layout of the multi-layer film (F) (from interior (in contact with the cosmetic composition (KM)) to exterior):

-   -   a) *Interior*-Layer (P1)-Layer (P2)-Barrier layer         (BS)-*Exterior*,     -   b) *Interior*-Layer (P1)-Barrier layer (BS)-Layer         (P2)-*Exterior*,     -   c) *Interior*-Layer (P2)-Layer (P1)-Barrier layer         (BS)-*Exterior*,     -   d) *Interior*-Layer (P2)-Barrier layer (BS)-Layer         (P1)-*Exterior*,     -   e) *Interior*-Barrier layer (BS)-Layer (P1)-Layer         (P2)-*Exterior*,     -   f) *Interior*-Barrier layer (BS)-Layer (P2)-Layer         (P1)-*Exterior*,     -   g) *Interior*-Layer (P1)-Frst adhesive layer (SK1)-Layer         (P2)-Second adhesive layer (SK2)-Barrier layer (BS)-*Exterior*,     -   h) *Interior*-Layer (P1)-Adhesive layer (SK1)-Layer (P2)-Barrier         layer (BS)-*Exterior*,     -   i) *Interior*-Layer (P1)-Layer (P2)-Second adhesive layer         (SK2)-Barrier layer (BS)-*Exterior*,     -   j) *Interior*-Barrier layer (BS)-First adhesive layer         (SK1)-Layer (P1)-Second adhesive layer (SK2)-Layer         (P2)-*Exterior*,     -   k) *Interior*-Barrier layer (BS)-Adhesive layer (SK)-Layer         (P1)-Layer (P2)-*Exterior*,     -   l) *Interior*-Barrier layer (BS)-Layer (51)-Adhesive layer         (SK)-Layer (P2)-*Exterior*,     -   m) *Interior*-Layer (P1)-First adhesive layer (SK1)-Barrier         layer (BS)-Second adhesive layer (SK2)-Layer (P2)-*Exterior*,     -   n) *Interior*-Layer (P1)-Adhesive layer (SK)-Barrier layer         (BS)-Layer (P2)-*Exterior*,     -   o) *Interior*-Layer (P1)-Barriere Layer (BS)-Adhesive layer         (SK)-Layer (P2)-*Exterior*.

The products obtained in this way have a high storage stability and a water loss during storage that is within an acceptable range. No swelling or delamination of the packaging (VP) during storage of these cosmetic products as contemplated herein was observed.

The product as contemplated herein is used for the purpose of oxidative color change. For this purpose, the composition (KM) packaged in the packaging (VP), which is the oxidizing agent composition, is mixed with at least one further composition (B) to produce the ready-to-use color changing agent. To prevent incompatibilities or premature reaction, the compositions (KM) and (B) are packaged separately.

A particularly preferred product as contemplated herein is exemplied in that it comprises a composition (B) separately prepared from composition (KM), wherein composition (B) contains at least one compound selected from oxidative colorant precursor, direct dyes, alkalizing agents and mixtures thereof. Preferred products of the present disclosure additionally comprises at least one second cosmetic composition (KM2) which contains at least one compound selected from oxidative colorant precursor, direct dyes, alkalizing agents and mixtures thereof and which is packaged separately from the cosmetic composition (KM).

If oxidative coloration is desired, composition (B) contains at least one oxidative colorant precursor. Oxidative colorant precursors may be divided into developers and couplers, whereby the developers are usually used in the form of their physiologically compatible salts (e.g. in the form of their hydrochlorides, hydrobromides, hydrogen sulfates or sulfates) due to their greater sensitivity to oxygen. Coupler components alone do not form a significant coloration in the course of oxidative coloration, but always require the presence of developer components. Preferably such agents contain at least one oxidative colorant precursor of the developer type and at least one oxidative colorant precursor of the coupler type. Particularly suitable oxidative colorant precursors of the developer type are selected from at least one compound from the group formed by p-phenylenediamine, p-toluenediamine, 2-(2-hydroxyethyl)-p-phenylenediamine, 2-(1,2-dihydroxyethyl)-p-phenylenediamine, N,N-bis-(2-hydroxyethyl)-p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine N,N′-bis-(2-hydroxyethyl)-N,N′-bis-(4-aminophenyl)-1,3-diamino-propan-2-ol, bis-(2-hydroxy-5-aminophenyl)methane, 1,3-bis-(2,5-diaminophenoxy)propane-2-ol, N,N′-bis-(4-aminophenyl)-1,4-diazacycloheptane, 1,10-bis-(2,5-diaminophenyl)-1,4,7,10-tetraoxadecane p-Aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(1,2-dihydroxyethyl)phenol, 4-amino-2-(diethylaminomethyl)phenol 4,5-diamino-1-(2-hydroxyethyl)pyrazole, 2,4,5 ,6-tetraamino-pyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triamino-pyrimidine, 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-on and their physiologically compatible salts.

Particularly suitable oxidative colorant precursors of the coupler type are selected from the group formed by 3-aminophenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro-2-methylphenol, 5-(2-hydroxyethyl)-amino-2-methylphenol, 2,4-dichloro-3-aminophenol, 2-aminophenol, 3-phenylene-diamine, 2-(2,4-diaminophenoxy)ethanol, 1,3-bis(2,4-diaminophenoxy)propane, 1-methoxy-2-amino-4-(2-hydroxyethylamino)benzene, 1,3 -bis(2,4-diaminophenyl)propane, 2,6-bis(2′-hydroxyethylamino)-1-methylbenzene, 2-({3-[(2-hydroxyethyl) amino]-4-methoxy-5-methylphenyl}amino)ethanol, 2-({3-[2-hydroxyethyl)amino]-2-methoxy-5-methylphenyl}amino)ethanol, 2-({3-[2-hydroxyethyl)amino]-4,5-dimethylphenyl}amino)ethanol, 2-[3-morpholin-4-ylphenyl)amino]ethanol, 3-amino-4-(2-methoxy-ethoxy)-5-methylphenylamine, 1-amino-3-bis-(2-hydroxyethyl)aminobenzene, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 1,2,4-trihydroxybenzene, 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-phenyl-3-methylpyrazol-5-on, 1-naphthol, 1,5-dihydroxy-naphthalene, 2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxy-naphthalene, 4-hydroxy-indole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindoline or mixtures of these compounds or their physiologically acceptable salts.

In addition, the composition (B) may also contain one or more direct dyes. Suitable non-ionic direct dyes may be selected from the group HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 7, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis(2-hydroxyethyl)-amino-2-nitrobenzene, 3-nitro-4-(2-hydroxyethyl)aminophenol, 2-(2-hydroxyethyl)amino-4,6-dinitro-phenol, 4-[(2-hydroxyethyl) amino]-3 -nitro-1-methylbenzene, 1-amino-4-(2-hydroxyethyl)amino-5-chloro-2-nitrobenzene, 4-amino-3 -nitrophenol, 1-(2′-ureidoethyl)amino-4-nitrobenzene, 2-[(4-amino-2-nitrophenyl)amino]benzoic acid, 4-[(3-hydroxypropyl)amino]-3 -nitrophenol, 4-nitro-o-phenylenediamine, 6-nitro-1,2,3,4-tetrahydroquinone, 2-hydroxy-1,4-naphthoquinone, picramine acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoe acid and 2-chloro-6-ethylamino-4-nitrophenol.

Suitable anionic direct dyes may be selected from the group of Acid Yellow 1, Yellow 10, Acid Yellow 23, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 52, Pigment Red 57:1, Acid Blue 7, Acid Green 50, Acid Violet 43, Acid Black 1, Acid Black 52, Bromophenol Blue and Tetrabromophenol Blue.

Suitable cationic direct dyes are cationic triphenylmethane dyes, such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14, aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, cationic anthraquinone dyes, such as HC Blue 16 (Bluequat B), and direct dyes containing a heterocycle containing at least one quaternary nitrogen atom, in particular Basic Yellow 87, Basic Orange 31 and Basic Red 51. The cationic direct dyes marketed under the trademark Arianor are also suitable cationic direct dyes as contemplated herein.

Dyeing processes on keratinous fibers are usually carried out in an alkaline environment. In order to protect the keratinous fibers and also the skin as much as possible, however, the adjustment of a too high pH value is not desirable. Therefore, it is preferable if the pH value of composition (B) is between about 7 and about 11, especially between about 8 and about 10.5. For the purposes of the present disclosure, the pH values are pH values measured at a temperature of about 22° C.

Composition (B) may contain at least one alkalizing agent. The alkalizing agents usable for adjusting the preferred pH value as contemplated herein may be selected from the group formed by ammonia, alkanolamines, basic amino acids, and inorganic alkalizing agents such as (earth) alkali metal hydroxides, (earth) alkali metal metasilicates, (earth) alkali metal phosphates and (earth) alkali metal hydrogen phosphates. Preferred inorganic alkalizing agents are magnesium carbonate, sodium hydroxide, potassium hydroxide, sodium silicate and sodium metasilicate. Organic alkalizing agents which can be used as contemplated herein are preferably selected from monoethanolamine, 2-amino-2-methyl-propanol and triethanolamine The basic amino acids usable as alkalizing agents as contemplated herein are preferably selected from the group formed from arginine, lysine, ornithine and histidine, especially preferably arginine. However, in the course of the investigations into the present disclosure, it was found that further agents as contemplated herein additionally contain an organic alkalizing agent. An embodiment of the present disclosure is exemplified in that the agent additionally contains at least one alkalizing agent selected from the group formed by ammonia, alkanolamines and basic amino acids, in particular ammonia, monoethanolamine and arginine or its compatible salts.

The composition (B) may further contain additional active ingredients, auxiliary substances and additives. For example, one or more fat components from the group of C₁₂-C₃₀ fatty alcohols, C₁₂-C₃₀ fatty acid triglycerides, C₁₂-C₃₀ fatty acid monoglycerides, C₁₂-C₃₀ fatty acid diglycerides and/or hydrocarbons may be included.

Preferably, a surface-active substance may be added to composition (B), whereby such surface-active substances are referred to as surfactants or emulsifiers, depending on the area of application: they are preferably selected from anionic, zwitterionic, amphoteric and non-ionic surfactants and emulsifiers.

The composition (B) preferably contains at least one anionic surfactant. Preferred anionic surfactants are fatty acides, alkyl sulfates, alkyl ether sulfates and ether carbon acids with 10 to 20 carbon atoms in the alkyl group and up to 16 glycol ether groups in the molecule.

Furthermore, composition (B) may additionally contain at least one zwitterionic surfactant. Preferred zwitterionic surfactants are betaines, N-alkyl-N,N-dimethylammonium-glycinate, N-acyl-aminopropyl-N,N-dimethylammoniumglycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines. A preferred zwitterionic surfactant is known under the INCI designation Cocamidopropyl Betaine.

Furthermore, it may be intended that the composition (B) contains at least one amphoteric surfactant. Preferred amphoteric surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkyl-amino butter acids, N-alkyl amino dipropion acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkyl amino propionic acids and alkyl amino acetic acids. Particularly preferred amphoteric surfactants are N-coconut alkylaminopropionate, as coconut acylaminoethylamino propionate and C₁₂-C₁₈ acyl sarcosine.

Furthermore, it has proven to be advantageous if the composition (B) contains further, non-ionic surface-active substances. Preferred non-ionic surfactants are alkyl polyglycoside and alkylene oxide plant products on fatty alcohols and fatty acids with 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid. Compositions with outstanding properties are also obtained if they contain fatty acid esters of ethoxylated glycerol as non-ionic surfactants.

The non-ionic, zwitterionic or amphoteric surfactants are used in proportions of from about 0.1 to about 45% by weight, preferably from about 1 to about 30% by weight and particularly preferably from about 1 to about 15% by weight, based on the total weight of the composition (B).

Composition (B) may also contain at least one thickening agent. There are no restrictions in principle with regard to these thickening agents. Both organic and purely inorganic thickening agents may be used. Suitable thickening agents are anionic, synthetic polymers, cationic, synthetic polymers, naturally occurring thickening agents such as non-ionic guar gums, scleroglucan gums or xanthane gums, gum arabicum, ghatti gum, karaya gum, tragacanth gum, carrageenan gum, agar-agar, carob bean gum, pectins, alginates, starch fractions and derivatives such as amylose, amylo-pectin and dextrine, as well as cellulose derivatives such as methyl cellulose, carboxyalkyl celluloses and hydroxyalkyl celluloses, non-ionic, fully synthetic polymers such as polyvinyl alcohol or polyvinyl pyrrolidinone as well as inorganic thickening agents, in particular phyllosilicates such as bentonite, especially smectites such as montmorillonite or hectorite.

Furthermore, composition (B) may contain other active ingredients, auxiliary substances and additives, such as non-ionic polymers such as vinyl pyrrolidine/vinyl acrylat copolymers, polyvinyl pyrrolidinone, vinyl pyrrolidine/vinyl acetate copolymers, polyethylene glycols and poly-siloxanes; additional silicones such as volatile or non-volatile, straight-chain, branched or cyclic, crosslinked or non-crosslinked polyalkylsiloxanes (such as dimethicones or cyclomethicones), polyarylsiloxanes and/or polyalkylarylsiloxanes, in particular polysiloxanes with organo-functional groups, such as substituted or unsubstituted amines (amodimethicones), carboxyl, alkoxy and/or hydroxyl groups (dimethicone copolyols), linear polysiloxane(A)-polyoxyalkylene(B) block copolymers, grafted silicone polymers; cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamidedimethyldiallylammonium chloride copolymers, dimethylamino-ethyl methacrylate-vinylate vinyl pyrrolidinone copolymers quaternized with diethyl sulfate, vinyl pyrrolidinone-imidazolium methochloride copolymers and quaternized polyvinyl alcohol; zwitterionic and amphoteric polymers; anionic polymers such as, for example, polyacrylacids or cross-linked polyacrylics; structurants such as glucose, maleic acid and lactic acid, hair-conditioning compounds such as phospholipids, for example lecithin and cephalins; perfume oils, dimethyl iso-sorbide and cyclodextrins; fiber structure-improving active substances, in particular mono-, di- and oligo-saccharides such as glucose, galactose, fructose, fructose and lactose; dyes for colouring the composition; anti-dandruff active substances such as piroctone olamines, zinc omadine and climbazole; amino acids and oligopeptides; animal and/or vegetable-based protein hydrolysates, as well as in the form of their fatty acid condensation products or optionally anionically or cationically modified derivatives; fatty substances and vegetable oils; sunscreens and UV blockers; active ingredients such as panthenol, panthenic acid, pantolactone, allantoin, pyrrolidinone-carbon acid and its salts, and bisabolol; polyphenols, in particular hydroxyzimt acids, 6,7-dihydroxycoumarins, hydroxybenzoeacids, catechins, tannins, leucoanthocyanidins, anthocyanidins, flavanones, flavones and flavonols; ceramides or pseudoceramides; vitamins, provitamins and vitamin precursors; plant extracts; fats and waxes such as fatty alcohols, beeswax, montan wax and paraffins; swelling and penetrating agents such as glycerine, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas as well as primary, secondary and tertiary phosphates; anti-caking agents such as latex, styrene/PVP and styrene/acrylamide copolymers; pearlescent agents such as ethylene glycol mono- and distearate as well as PEG-3 distearate and pigments.

The selection of these additional substances will be made by the expert according to the desired properties of the composition (B) as well as the product as contemplated herein. With regard to further optional components and the quantities of these components used, explicit reference is made to the relevant handbooks known to the expert. The additional active ingredients and auxiliary substances are preferably used in the composition (B) in quantities of from about 0.0001 to about 25% by weight each, in particular from about 0.0005 to about 15% by weight, in each case based on the total weight of the composition (B).

The following examples explain the present disclosure without limiting it:

EXAMPLES

A 100 nm thick layer of aluminum was vapor-deposited onto a film layer of biaxially oriented polypropylene with a thickness of 12 μm (micrometer). The aluminum layer was then painted over with approx. 3 g/m² of ORMOCER polymer and cured. A 70 μm (micrometer) thick layer of polyethylene was then applied to the ORMOCER layer. A packaging (VP) was produced from the film. The film is also provided with a PET layer 20 μm thick.

The packaging (VP) was filled with the following composition (KM1) (all figures in % by weight). The oxidizing agent is preferably hydrogen peroxide.

Ingredients KM1 Potassium hydroxide (50%) 0.66 Dipicolin acid 0.10 Disodium pyrophosphate 0.030 1-hydroxyethan-1,1-diphosphon acid (60%) 1.5 Keltrol CG-SFT (xanthane) 2.0 H₂O₂ 50% (oxidizing agent) 8.2 1,2-propanediol 4.0 Water ad 100

The cosmetic composition KM1 was filled into the packaging (VP) described above. The packaging was then stored at 40° C. for 24 weeks. The packages were not inflated or delaminated.

While at least one exemplary embodiment has been presented in the foregoing detailed description, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the various embodiments in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment as contemplated herein. It being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope of the various embodiments as set forth in the appended claims. 

1. Cosmetic product for modifying the natural color of keratinous fibers, comprising (i) at least one packaging comprising at least one multi-layer film comprising at least one first polymer layer, at least one second polymer layer and at least one barrier layer, and (ii) at least one cosmetic composition packaged and included in the packaging: a) at least one oxidizing compound and b) at least one thickening agent, selected from the group of xanthanes, wherein the first polymer layer is formed of polyethylene terephthalate or polyethylene naphthalate; the second polymer layer is formed of a polyolefin; and the barrier layer is formed of metallized oriented polypropylene.
 2. Cosmetic product according to claim 1, wherein the first polymer layer (has a layer thickness of from about 4 μm to about 50 μm; the second polymer layer (has a layer thickness of from about 20 μm to about 150 μm; and/or the layer thickness of the barrier layer is from about 4 μm to about 20 μm.
 3. Cosmetic product according to claim 1, wherein the multi-layer film has an Oxygen Transmission Rate at about 23° C. and about 50% relative humidity of from about 0.1 to about 5 cc/m²/d/bar and has a water vapor permeability at about 38° C. and about 100% relative humidity of from about 0.1 to about 5 g/m² d.
 4. Cosmetic product according to claim 1, wherein the adhesive strength of the film is from about 0.1 to about 10 N/15 mm.
 5. Cosmetic product according to claim 1, wherein the seal strength of the packaging is from about 10 to about 40 N/15 mm under the conditions of about 150° C., about 2.54 cm (1″) and about 4 kg/cm².
 6. Cosmetic product according to claim 1, wherein the at least one multi-layer film comprises the at least one barrier layer between the at least one first polymer layer and the at least one second polymer layer.
 7. Cosmetic product according to claim 1, wherein the first polymer layer forms the outer layer.
 8. Cosmetic product according to cl aim 1, wherein the cosmetic composition comprises at least one oxidizing compound, in a total amount of from about 0.5 to about 20% by weight, relative to the total weight of the cosmetic composition.
 9. Cosmetic product according to claim 1, wherein the cosmetic composition has a pH value (measured at about 20° C.) of about pH 1.5 to about pH 5.0.
 10. Cosmetic product according to claim 1, wherein the cosmetic composition comprises at least one thickening agent chosen from the group of xanthanes in a total amount of from about 0.1 to about 10% by weight, relative to the total weight of the cosmetic composition.
 11. Cosmetic product according to claim 1, wherein the first polymer layer has a layer thickness of from about 6 μm to about 20 μm; the second polymer layer has a layer thickness of from about 40 μm to about 90 μm; and/or the layer thickness of the barrier layer is from about 6 μm to about 15 μm.
 12. Cosmetic product according to claim 11, wherein the multi-layer film has an Oxygen Transmission Rate at about 23° C. and about 50% relative humidity of from about 0.5 to about 2.5 cc/m²/d/bar and has a water vapor permeability at about 38° C. and about 100% relative humidity of from about 0.5 to about 2.5 g/m² d.
 13. Cosmetic product according to claim 1, wherein the multi-layer film has an Oxygen Transmission Rate at about 23° C. and about 50% relative humidity of from about 0.5 to about 2.5 cc/m²/d/bar and has a water vapor permeability at about 38° C. and about 100% relative humidity of from about 0.5 to about 2.5 g/m² d.
 14. Cosmetic product according to claim 1, wherein the adhesive strength of the film is from about 1.5 to about 5 N/15mm.
 15. Cosmetic product according to claim 1, wherein the seal strength of the packaging is from about 20 to about 30 N/15mm under the conditions of about 150° C., about 2.54 cm (1″) and about 4 kg/cm².
 16. Cosmetic product according to claim 1, wherein the at least one multi-layer film comprises the at least one barrier layer between the at least one first polymer layer and the at least one second polymer layer.
 17. Cosmetic product according to claim 1, wherein the first polymer layer forms the outer layer.
 18. Cosmetic product according to claim 1, wherein the cosmetic composition comprises at least one oxidizing compound in a total amount of from about 1.5 to about 15% by weight relative to the total weight of the cosmetic composition.
 19. Cosmetic product according to claim 1, wherein the cosmetic composition has a pH value (measured at about 20° C.) of about pH 2.5 to about pH
 4. 20. Cosmetic product according to claim 1, wherein the first polymer layer is formed of polyethylene terephthalate and the second polymer layer (P2) is formed of polyethylene; the first polymer layer has a layer thickness of from about 6 μm to about 20 μm; the second polymer layer has a layer thickness of from about 40 μm to about 90 μm; and/or the layer thickness of the barrier layer is from about 6 μm to about 15 μm; the multi-layer film has an Oxygen Transmission Rate at about 23° C. and about 50% relative humidity of from about 0.5 to about 2.5 cc/m²/d/bar and has a water vapor permeability at about 38° C. and about 100% relative humidity of from about 0.5 to about 2.5 g/m² d; the adhesive strength of the film is from about 1.5 to about 5 N/15 mm; the seal strength of the packaging is from about 20 to about 30 N/15 mm under the conditions about 150° C., about 2.54 cm (1″) and about 4 kg/cm²; the at least one multi-layer film comprises the at least one barrier layer between the at least one first polymer layer and the at least one second polymer layer; the first polymer layer forms the outer layer; the cosmetic composition comprises hydrogen peroxide in a total amount of from about 1.5 to about 15% by weight relative to the total weight of the cosmetic composition; the cosmetic composition has a pH value (measured at about 20° C.) of about pH 2.5 to about pH 4; and the cosmetic composition comprises at least one thickening agent chosen from the group of xanthanes in a total amount of from about 0.2 to about 6% by weight relative to the total weight of the cosmetic composition. 